Two- and three-photon resonant ionization spectroscopy is used to explore the high-lying electronic states of octafluorocyclooctatetraene (OFCOT). CNDO/S calculations are reported as an aid in the assignment of the observed valence transitions. The spectra agree quite well with the predictions of the semi-empirical method, which has not been previously tested at such high energies. The ionization potential for this molecule is estimated and the effects of “through-space” and “through-bond” coupling on the energy levels are discussed. Comparison is made to the already reported spectroscopy of the hydrocarbon analog.